Non-volatile resistance switching memory

ABSTRACT

A microelectronic device or non-volatile resistance switching memory comprising the switching material for storing digital information. A process includes a step of depositing the switching material by a CMOS deposition technique at a temperature lower than 400° C.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a division of, and claims priority from,commonly-owned, co-pending U.S. patent application Ser. No. 11/105,849,filed on Apr. 14, 2005; which application is incorporated by referencein its entirety as if fully set forth herein.

TECHNICAL FIELD

The present invention is related to a process for depositing a switchingmaterial that is switchable between conductivity states and where thestates are persistent. The invention further relates to amicroelectronic device or non-volatile resistance switching memorycomprising the switching material for storing digital information.

BACKGROUND OF THE INVENTION

Non-volatile resistance switching memory, particularly memory based oncomplex metal oxides, is typically either deposited at high temperature,usually at about 800° C., or requires high temperature post-depositionannealing. This makes it impossible to integrate this type of memory ina back end of the line (BEOL) process with standardcomplementary-metal-oxide-semiconductor (CMOS) technology. For far BEOLintegration the allowed temperatures are even more stringent.

Liu et al., Electrical-pulse-induced reversible resistance change effectin magnetoresistive films, Applied Physics Letters, 76, 2749, 2000 andthe international publication WO00/15882 relate to a perovskite layerdeposited epitaxially (single crystalline) at elevated temperature bypulsed laser deposition on a substrate. This deposition technique cannotbe used for standard CMOS technology.

US20030148545A1 shows a way of manufacturing a variable resistor devicebased on poly-crystalline perovskite metal oxides using spin-coatingdeposition techniques. Silicon substrates can be used with thetechniques of manufacturing. An annealing process step of thespin-coated layer between 400° C. and 700° C. is however required toobtain switching between a first resistance state and a secondresistance state in the respective devices.

From the above it follows that there is still a need in the art for aprocess for manufacturing resistance switching memory based on a complexmetal oxide such that (far) BEOL integration with standard CMOStechnology becomes possible.

SUMMARY OF THE INVENTION

Thus, in accordance with the present invention, there is provided aprocess for depositing a switching material that is switchable betweenat least a first conductivity state and a second conductivity state,each of the states being persistent. The process comprising a step ofdepositing the switching material by a standardcomplementary-metal-oxide-semiconductor (CMOS) deposition technique at atemperature lower than 400° C. In other words, the switching material isdeposited such as to form an essentially amorphous or poly-crystallinelayer. That is, the switching material has an amorphous orpoly-crystalline structure resulting from the used depositiontemperature. The process can be used for manufacturing microelectronicdevices comprising a non-volatile resistance switching memory elementbetween two electrodes.

In accordance with a second aspect of the present invention, there isprovided a microelectronic device for storing digital informationcomprising a switching material deposited according to the disclosedprocess.

The process of the present invention allows that all steps can beperformed at temperatures below 400° C. This makes the preferred (far)BEOL integration of non-volatile resistance switching memory based oncomplex metal oxides with standard CMOS technology possible.

In an advantageous embodiment radio frequency (RF) sputtering is used asthe PVD technique because it is a reliable deposition process with highwafer throughput and cost effective manufacturing. DC sputtering mightalso be applied.

DESCRIPTION OF THE DRAWINGS

Advantageous embodiments of the invention are described in detail below,by way of example only, with reference to the following drawings.

FIG. 1 shows a schematic drawing of a microelectronic device having anon-volatile resistance switching memory element.

FIG. 2(A) shows an X-ray diffraction spectrum (Cu Kα, λ=1.5406 Å) of anamorphous Cr-doped SrTiO₃ layer deposited at T=100° C.

FIG. 2(B) shows an X-ray diffraction spectrum (Cu Kα, λ=1.5406 Å) of apoly-crystalline Cr-doped SrTiO₃ layer deposited at T<400° C. Braggpeaks are indexed in the conventional (h,k,l)-notations.

FIG. 3 shows a typical reversible switching between a first resistancestate and a second resistance state, each of the two states beingpersistent, of a device having a switching member comprising anessentially amorphous Cr-doped SrTiO₃ layer deposited at T=100° C.

FIGS. 4(A) and 4(B) show the endurance of the first resistance state andthe second resistance state, respectively, each of the two states beingpersistent, of the device having a switching member with an essentiallyamorphous Cr-doped SrTiO₃ layer deposited at T=100° C.

FIG. 5 shows a bit-error-rate of the device with a switching membercomprising an essentially amorphous Cr-doped SrTiO₃ layer deposited atT=100° C.

FIG. 6 shows reversible switching between a first resistance state and asecond resistance state, each of the two states being persistent, of thedevice having a switching member with an essentially amorphous Cr-dopedSrTiO₃ layer deposited at T=100° C. for optimized control currentconditions.

The drawings are provided for illustrative purposes only.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides a process for depositing a switchingmaterial that is switchable between at least a first conductivity stateand a second conductivity state, each of the states being persistent. Anexample of a process comprises a step of depositing the switchingmaterial by a standard complementary-metal-oxide-semiconductor (CMOS)deposition technique at a temperature lower than 400° C. In other words,the switching material is deposited such as to form an essentiallyamorphous or poly-crystalline layer. That is, the switching material hasan amorphous or poly-crystalline structure resulting from the useddeposition temperature.

The process can be used for manufacturing microelectronic devicescomprising a non-volatile resistance switching memory element betweentwo electrodes. The switching material provides the functionality of thenon-volatile resistance switching memory element, herein also referredto as switching member or switching layer. The switching layer can beformed on a substrate by physical vapor deposition (PVD) at atemperature lower than 400° C. This has the advantage that no annealingprocesses are required afterwards. The switching member layer can beessentially amorphous or poly-crystalline. Its resistance can bereversibly switched between at least a first resistance state and asecond resistance state, each of the at least two states beingpersistent. The switching of the resistance between the first and secondresistance state can be controlled by electrical voltage or currentpulses.

In accordance with a second aspect of the present invention, there isprovided a microelectronic device for storing digital informationcomprising a switching material deposited according to the disclosedprocess.

The disclosed process allows that all process steps can be performed attemperatures at, below and above 400° C. This makes the preferred (far)BEOL integration of non-volatile resistance switching memory based oncomplex metal oxides with standard CMOS technology possible. When afterthe deposition step no annealing process step is applied, then the totalprocessing time can be reduced and the manufacturing time ofmicroelectronic devices having the deposited switching material can beshortened. Moreover the manufacturing cost can be reduced. The switchingmaterial is reversibly switchable between at least a first conductingstate and a second conducting state.

Physical vapor deposition (PVD) can be used as deposition technique forthe switching material, but also metal organic chemical vapor deposition(MOCVD) can be used. Molecular Beam Epitaxy (MBE) might also be applied.

In PVD atoms of a heavy, but inert gas, typically argon, areelectrically accelerated towards a target. These atoms chip off or“sputter” the target material, atom by atom. The sputtered atom lands onthe wafer surface, where it forms a solid layer. In metal organicchemical vapor deposition (MOCVD) a gas containing a metal and/orinsulator chemistry is sprayed on the wafer. These gases react on thewafer surface, forming a thin film of solid material. Energy sourcessuch as heat and radio frequency power are used alone or in combinationto achieve this reaction.

In an advantageous embodiment radio frequency (RF) sputtering is used asPVD technique because it is a reliable deposition process with highwafer throughput and cost effective manufacturing. DC sputtering mightalso be applied.

A transition metal oxide can be used as the switching material that isalso referred to as perovskite, complex metal oxide, or complex metaloxide resistance switching material, which, for example, can compriseSrTiO₃ doped with Chromium (Cr) or SrZrO₃ doped with Cr. As analternative to Cr other transition metal elements could be used.

The switching material can be deposited on a substrate having atemperature between approximately room temperature and 400° C. Thedeposition of the switching material can be performed belowapproximately 100° C. Then, the switching material is essentiallyamorphous whilst a deposition at approximately 400° C. leads to aswitching material having a poly-crystalline structure which could alsobe desired.

It is advantageous to deposit the switching material at roomtemperature. This does not require any heating.

FIG. 1 shows a schematic sectional view of a non-volatile resistanceswitching memory device 10 having a capacitor-like structure. Such amicroelectronic device is useable as a memory cell or within an array ascross-point memory. On a substrate 18 a stack-like arrangement of afirst or base electrode 12, a non-volatile resistance switching memoryelement or switching member 14, and a second or top electrode 16 isformed. An insulating buffer layer 11 may be included between thesubstrate 18 and the first electrode 12. One terminal 20 is connected tosaid top electrode 16, the other terminal 22 is connected to the firstelectrode 12. The leakage current can be measured as it is depicted inthe drawing as a function of the bias voltage generated by a DC voltagesource 24 between said terminals 20, 22. In an experimental arrangementsetup for testing the basic switching behavior and further physicalproperties of the device 10 the switching member layer thickness wasapproximately 150 nanometers.

The switching member's resistance can be reversibly switched between atleast a first resistance state and a second resistance state; therebyeach of the states is persistent. The switching of the resistancebetween the first and second resistance state is controlled by, forexample, electrical voltage or current pulses as described in theinternational application with publication no. WO 00/49659, presentlyassigned to the assignee of the instant application and the disclosureof which is incorporated herein by reference.

A variety of materials can be used advantageously for the substrate 18,the insulating buffer layer 11, the first electrode 12, the switchingmember 14, and the second electrode 16. For a stand-alone non-volatileresistance switching memory application the substrate 18 may consist ofSilicon or Silicon on Insulator (SOD wafers. Other substrates such asSilicon Germanium, Gallium Arsenide, non-crystalline materials, i.e.glass, or Quartz wafers could also be considered. For an embeddednon-volatile resistance switching memory application Silicon (or SOI)wafers that are processed up to the BEOL in a standard CMOS logicprocess could be used as substrate 18.

The compound that is deposited as the first electrode layer may be anynumber of different types of metals, such as Pt, Ti, W, Ta, Ru, Cu,semiconductor, metallic oxide, etcetera. Conventional methods ofdeposition, such as physical vapor deposition or chemical vapordeposition may be used to deposit the first electrode layer. Otherpossibilities for the first electrode 12 include aluminum that has longbeen the conductor of choice for standard CMOS technology, or thecurrent material of choice for on-chip metallization, Damasceneelectroplated copper. Other metals may also be used as first electrodelayer. A chemical-mechanical polishing process may be included forplanarizing or removing excess material from the surface of the wafer.This process step presents a smooth top surface for further processing.

The switching member 14 or switching member layer 14 is prepared byphysical vapor deposition (PVD). PVD is a reliable production processwith typically high wafer throughput and cost effective manufacturing. Apreferred PVD production tool meets the international SEMATECHperformance metrics and factory guidelines for CMOS semiconductorfactories.

Immediately prior to the PVD process the wafers 18 are preferablycleaned in-situ. The wafers may be degassed in vacuum with radiationheaters. In addition typically a plasma sputtering step or reactive ionetching cleaning process is included to assure clean surfaces and goodadhesion. For example, a plasma sputter cleaning process could include afew minutes inverse sputter etching in Argon (Ar) plasma, with a 13.56MHz radio frequency (RF) power of 100 W on 8 inch, while a pressure of 6gbar is maintained in the vacuum chamber. The pre-clean etch uniformitytotal variability is preferentially below 3% (3σ). For example, the PVDprocess to deposit the switching member layer 14 can be done under acondition in which the wafer temperature is between approximately roomtemperature and 400° C. The base pressure of the vacuum system ispreferably below 10.sup.-5 mbar. The RF power may be controlled between100 and 2000 W. In addition a RF bias can be applied to tune thedeposited layer compressive stress on Si wafers to values between 0 and300 MPa. The pressure range can be maintained between about 1 μbar and50 μbar. A mixture of at least Ar and Oxygen (O₂) gasses is used in thesputtering process. Suitable gas ratios Ar:O₂ range between 5:1 and 1:5.The flow rate of Ar and O₂ typically is between 1 and 100 sccm. The PVDprocess target for the switching member thickness can be chosen betweenabout 10 nm and 1 μm. The advantageous film thickness uniformity totalvariability is below 3% (3σ).

Good results have particularly been achieved using sintered sputteringtargets comprising stoichiometric SrTiO₃, SrZrO₃, other materials withperovskite structure, or perovskite-like structure, or combinationsthereof, each material preferably doped with up to about 20% Cr, V, orMn. Advantageously the chemical purity of the target is at least 2N8.

In an advantageous embodiment the switching member 14 as anapproximately 150 nm thick layer of SrTiO₃ doped with 0.2 mol % Cr orSrZrO₃ doped with 0.2 mol % Cr is deposited at a temperature of 100° C.A mixture of Ar and O₂ with ratio 1:1 is used for the sputteringprocess. A 13.56 MHz RF power of 600 W on the 8 inch target is used. Thepressure during PVD is maintained at 20 μbar. The compressive stress inthe characteristic switching layer is about 50 MPa. No further annealingprocess steps are required.

The metal that is deposited for the second electrode 16 may be anynumber of different types of metals, such as Pt, Ti, W, Ta, Ru, Al, Cu,and so forth. Conventional methods of low temperature deposition may beused to deposit the top electrode layer. Other metals may also be usedas second electrode layer.

FIG. 2(A) displays an X-ray diffraction spectrum (Cu Kα, λ=1.5406 Å) ofan approximately 150 nm thick layer of the switching member 14. In thiscase a Cr-doped SrTiO₃ layer was deposited at T=100° C. No Bragg peaks,apart from the substrate diffraction peak, are present. This indicatesthat the deposited Cr-doped SrTiO₃ switching member is essentiallyamorphous.

FIG. 2(B) displays an X-ray diffraction pattern (Cu Kα, λ=1.5406 Å) ofan approximately 150 nm thick layer of the switching member 14. In thiscase a Cr-doped SrTiO₃ layer was deposited at T<400° C. The diffractionspectrum of a poly-crystalline perovskite is obtained; this indicatesthat the deposited Cr-doped SrTiO₃ switching member is essentiallypoly-crystalline.

As mentioned above, the reversible switching of the resistance between afirst resistance state and a second resistance state is controlled by,for example, electrical voltage or current pulses as described in theinternational application with publication no. WO 00/49659.

FIG. 3 shows a typical reversible switching between a first resistancestate and a second resistance state of the non-volatile resistanceswitching memory device 10, each of the two states being persistent,comprising an essentially amorphous Cr-doped SrTiO₃ switching memberdeposited at T=100° C. The first and second electrode 12, 16 is 100 nmPt deposited at room temperate using PVD processes known in the art. Acurrent pulse of |I_(c)|.=0.5 mA between the first and second electrode12, 16 is used to control the resistance state of the device 10. Theresistance state is determined with a read voltage pulse of V_(read)=0.5V between the first and second electrode 12, 16. The device 10 has afirst resistance state of R₁˜3 kΩ and a second resistance state of R˜10kΩ; R₂/R₁˜3.

FIGS. 4(A) and 4(B) show the endurance of the first resistance state andthe second resistance state of the device 10, comprising the switchingmember 14 with the essentially amorphous Cr-doped SrTiO₃ layer depositedat T=100° C. The first and second electrode 12, 16 is 100 nm Ptdeposited at room temperate using PVD processes known in the art. 10⁵read voltage pulses of V_(read)=0.5 V are applied between the first andsecond electrode 12, 16 of 0.5 V to read the resistance state duringapproximately 2 hours. No control current pulses of |I_(c.)|=0.5 mA areapplied during this time. A narrow distribution of the resistance, orequivalently, the current flow, in the first and second state isobtained (σ₁=0.16 μA and ρ₂=0.18.μA).

FIG. 5 shows a bit-error-rate of the device 10 with the essentiallyamorphous Cr-doped SrTiO₃ switching layer deposited at T=100° C. Thefirst and second electrode 12, 16 is 100 nm Pt deposited at roomtemperate using PVD processes known in the art. A long sequence ofconsecutive write control current pulses of I_(c)=0.5 mA, read voltagepulses of V_(read)=0.5 V, erase control current pulses of I_(c)=−0.5 mA,and read voltage pulses of V_(read)=0.5 V is applied between the firstand second electrode 12, 16. A narrow distribution of the resistance, orequivalently, the current flow, in the first and second state isobtained (σ₁=0.5 μA and σ₂=0.3 μA). This shows that a well definedseparation of approximately 40σ between the two states can be obtainedwith the device 10 comprising the essentially amorphous Cr-doped SrTiO₃layer deposited at T=100° C.

The reversible switching of the resistance between a first resistancestate and a second resistance state can be further optimized by tuningthe control current pulses. FIG. 6 shows a reversible switching betweenthe first resistance state and the second resistance state of the device10 comprising the essentially amorphous Cr-doped SrTiO₃ switching layerdeposited at T=100° C. The first and second electrode 12, 16 is 100 nmPt deposited at room temperate using PVD processes known in the art. Acurrent pulse of |I|=1 mA between the first and second electrode 12, 16is used to control the resistance state of the device 10. The resistancestate is determined with a read voltage pulse of V_(read)=0.1 V betweenthe first and second electrode 12, 16. The device 10 has here a firstresistance state of R₁˜1 kΩ and a second resistance state of R₂˜200 kΩ;R₂/R₁˜200.

It is noted that any disclosed embodiment may be combined with one orseveral of the other embodiments shown and/or described. This is alsopossible for one or more features of the embodiments.

Variations described for the present invention can be realized in anycombination desirable for each particular application. Thus particularlimitations, and/or embodiment enhancements described herein, which mayhave particular advantages to the particular application need not beused for all applications. Also, not all limitations need be implementedin methods, systems and/or apparatus including one or more concepts ofthe present invention.

The present invention can be realized in hardware, or a combination ofhardware and software. A visualization tool according to the presentinvention can be realized in a centralized fashion in one computersystem, or in a distributed fashion where different elements are spreadacross several interconnected computer or other systems. Any kind ofcomputer system—or other apparatus adapted for carrying out the methodsand/or functions described herein—is suitable. A typical combination ofhardware and software could be a general purpose computer system with acomputer program that, when being loaded and executed, controls thecomputer system such that it carries out the methods described herein.The present invention can also be embedded in a computer programproduct, which comprises all the features enabling the implementation ofthe methods described herein, and which—when loaded in a computersystem—is able to control the carrying out of these methods. Computerprogram means or computer program in the present context include anyexpression, in any language, code or notation, of a set of instructionsintended to cause a system having an information processing capabilityto perform a particular function either directly or after conversion toanother language, code or notation, and/or reproduction in a differentmaterial form.

Thus the invention includes an article of manufacture which comprises acomputer usable medium having computer readable program code meansembodied therein for causing and controlling a function described above.The computer readable program code means in the article of manufacturecomprises computer readable program code means for causing a computer toeffect the steps of a method of this invention. Similarly, the presentinvention may be implemented as a computer program product comprising acomputer usable medium having computer readable program code meansembodied therein for causing a function described above. The computerreadable program code means in the computer program product comprisingcomputer readable program code means for causing a computer to effectone or more functions of this invention. Furthermore, the presentinvention may be implemented as a program storage device readable bymachine, tangibly embodying a program of instructions executable by themachine to perform method steps for causing control of one or morefunctions of this invention.

Thus, the invention includes a program storage device readable bymachine, tangibly embodying a program of instructions executable by themachine to perform steps for controlling deposition of a switchingmaterial. The steps of controlling are for controlling the method stepsof this invention.

The invention includes an apparatus comprising means for depositing aswitching material. The switching material being switchable between atleast a first conductivity state and a second conductivity state, eachof the states being persistent. The means for depositing comprisingmeans for depositing the switching material by a CMOS depositiontechnique at a temperature lower than 400° C.

The invention also includes a computer program product comprising acomputer usable medium having computer readable program code meansembodied therein for causing deposition of a switching material. Thecomputer readable program code means in the computer program productcomprising computer readable program code means for causing a computerto effect the control of functions of the present invention.

It is noted that the foregoing has outlined some of the more pertinentobjects and embodiments of the present invention. This invention may beused for many applications. Thus, although the description is made forparticular arrangements and methods, the intent and concept of theinvention is suitable and applicable to other arrangements andapplications. It will be clear to those skilled in the art thatmodifications to the disclosed embodiments can be effected withoutdeparting from the spirit and scope of the invention. The describedembodiments ought to be construed to be merely illustrative of some ofthe more prominent features and applications of the invention. Otherbeneficial results can be realized by applying the disclosed inventionin a different manner or modifying the invention in ways known to thosefamiliar with the art.

1. A program storage device readable by a computer, said device tangiblyembodying a program of instructions executable by the computer toperform steps for controlling deposition of a switching material, saidsteps of controlling comprising steps of: depositing over a substrate anon-volatile resistance switching transition metal oxide-material, saidswitching material being reversibly switchable between at least a firstconductivity state and a second conductivity state, each of the statesbeing persistent, wherein the transition metal oxide material isselected from the group consisting of SrTiO₃ doped with Chromium andSrZrO₃ doped with Chromium; wherein depositing the switching materialcomprises depositing said switching material by a CMOS depositiontechnique at a temperature lower than 100° C., using a mixture of atleast Argon and Oxygen gases in a range of Ar:O₂ between 5:1 and 1:5,giving said switching material an amorphous structure resulting from theused deposition temperature such that no post-deposition annealingprocess is required.